9-fluorene-beta-butyronitrile and method for its preparation



Patented Nov. 10, 1942 S-FLUOBENE-s-BUTYRONITBILE AND METHOD roa rrs PREPARATION Herman A. Bruson, Philadelphia, Pa., assignor to The Resinous Products a Chemical Company, Philadelphia, Pa, a corporation of Delaware No Drawing. Application November 12, 1941,

' Serial No. 418,855

4 Claims.

This invention relates to 9-iluorene-p-butyronitrlle AHA kid) CHa-H-CHsGN and a method for its preparation.

According to this invention, 9-iluorene-p-butyronitrile is prepared by condensing fluorene in the presence of an alkaline condensing agent with a member of the group consisting at allyl cyanide and crotononitrile.

.Among the alkaline condensing agents which can be used for promoting the reaction are the oxides, hydroxides, hydrides, amides, and alcoholates oi the alkali metals, or the alkali metals themselves. There may also be used strongly basic non-metallic hydroxides, such as the quaternary ammonium hydroxides. Of these, a particularly eii'ective product is the aqueous solution containing 40% of trimethyl benzyl ammonium hydroxide which is commercially available under the trade name Triton B." The quantity of alkaline condensing agent required is relatively small, amounts of the order of 1% to 10% on the combined weight the reactants being sufllcient. One or several of the alkaline condensing agents are suspended, or preierably dissolved, in a solution 01' the fluorene in an inert solvent, such as dioxane, benzene, or ether, and the crotononitrile or allyl cyanide gradually added thereto. The reaction takes place readily at temperatures between 0' and 80' C. It is conveniently started at room temperature and may be accelerated or completed by warming gently after the initial exothermal reaction has ceased.

The following example illustrates this invention, it being understood that alkalies, such as tetramethyl ammonium hydroxide, dimethyl dibenzyl ammonium hydroxide, sodium ter-butylate, sodium methylate, and the like, can be used in place or the preferred trimethyl benzyl ammonium hydroxide described below:

To a stirred solution oi 83 grams of fluorene, 250 grams of dioxane, and grams or aqueous 40% trimethyl benzyl ammonium hydroxide, there was added dropwise 67 grams of allyl cyanide during the course of one hour while the exothermal reaction was maintained at 38-47" C. by intermittent cooling. The mixture was then heated at 4550 C. for six hours longer, cooled, rendered faintly acid to Congo red indicator with dilute hydrochloric acid, taken up in its own volume oi ethylene dichloride and washed thoroughly with water. The ethylene dichloride layer was evaporated to dryness and the residual dark oil distilled under reduced pressure. After a small i'orerun of unchanged fluorene, the main fraction boiled between 190 and 220 C./1-2 mm. and weighed about grams. It formed a yellow balsam which gradually solidified to a crystalline mass. Upon recrystallization from methanol, the pure product was obtained in colorless crystals melting at 92-93 6., having the analysis Ci'IHrsN, corresponding to 9-fluorene-p-butyronitrile.

In place of allyl cyanide, one can employ crotononitrile in the same manner.

Q-fiuorene-fi-butyronitrile is useful as an intermediate for preparing drugs, plasticizers, and

resins. Upon hydrolysis, it yields the corresponding Q-fluorene-fl-butyramide or Q-fiuorene-pbutyric acid which may function as plant growth hormones for accelerating sprouting and rooting of plants.

I claim:

1. As a new compound, 9-fluorene-fi-butyronitrile having the formula:

CHa-CH-CIhGN onitrlle which comprises condensing fluorene in the presence of an alkaline condensing agent with allyl cyanide.

HERMAN A. BRUBON. 

